Heteroatom Rich Organic Polymers With Ultra-Small Pore Apertures For Carbon Dioxide Separation And/or Conversion
A heteroatom (N,S,O)-rich porous organic polymer and a membrane-based separation system and process employing the polymer is provided that utilizes one of a number of the heteroatom-rich porous organic polymers which contain ultra-small pores in their structures. The polymers can be used in the membranes to form a simpler, easy to regenerate separation system and method that and does not involve phase changes in the operation of the system. The system with the functionalized nanoporous organic polymer(s) can be utilized as a nanoporous membrane composite(s) for CO2 gas separation, or in the formation of a heterogeneous catalyst to convert CO2 to useful chemicals.
This application claims priority from U.S. Provisional Patent Application Ser. No. 62/610,183, filed on Mar. 18, 2016, the entirety of which is expressly incorporated herein by reference for all purposes.
FIELD OF THE INVENTIONThe present invention relates generally to porous organic polymers, and more specifically to heteroatom-rich porous organic polymers utilized in gas separation and in heterogeneous catalysts preparation.
BACKGROUND OF THE INVENTIONEnergy production and use account for two-thirds of the world's greenhouse-gas (GHG) emissions, In 2013, CO2 accounted for about 82% of all U, S, greenhouse gas emissions from human activities.1 Separation and capture of CO2, and its conversion to useful chemicals collectively is an important and promising way to address this urgent environmental challenge.
In 2010 the United States alone used 24.64 trillion cubic feet of natural gas. Such consumption of natural gas drives a worldwide market for new natural gas separation equipment of ˜$5 billion per year.2 In the production of natural gas, the natural gas or methane often has to be separated from other gases in order to enable the methane to be refined to a usable concentration or purity. Many different types of separation technologies are currently utilized to refine the methane from the other vases commonly produced along with methane, such as carbon dioxide.
For example, landfill gas, which is produced from municipal solid waste at landfills through microbial digestion, has been long-touted as a promising energy source. However, landfill gas is approximately 50% methane and 50% CO2, and CO2 removal from the methane remains a big hurdle to make this a potent, money-making energy source.
However, currently, amine scrubbers and cryogenic phase change processes are the most widely used technologies to separate CO2 from methane/CO2 gas mixtures. An amine scrubber uses asp alkanol amine solution in operation, which requires energy to regenerate the materials in the process and the amine solution is corrosive as well, rendering the material difficult to, handle.3 Further, the cryogenic gas-to-liquid phase change is highly energy- and capital intensive.4
In addition, a microbial pathway of conversion of CO2 to isoprene gas has recently been developed, with isoprene being a promising energy fuel.5, 6 However, the difficulty is how to separate the unreactive CO2 from the target product, isoprene, after completion of the process.
Thus, it is highly desirable to develop a method and system for removing CO2 from other gases, such as methane and isoprene, in a manner that does not require significant energy expenditure in order to more efficiently produce a useable gas stream(s) for energy production.
Recently, porous solid sorbents have emerged as promising materials to perform CO) capture and separation, heterogeneous catalysis, and sensing applications. In 2007, separation processes utilizing a membrane had less than 5% of this gas separation equipment market, almost all of which is applied toward the removal of carbon dioxide.2 The US membrane industry alone was forecast to spend $5.4 billion in 2016 alone as membrane technology continues to compete against typical absorption processes.7 However, current membrane separation technology, systems and processes are not capable of efficiently and reliably removing CO2 from a combined gas stream in order to produce an acceptable gas stream for energy production.
SUMMARY OF THE INVENTIONBriefly described, according to an exemplary embodiment of the invention we claim here the discovery of a series of nitrogen rich porous organic polymers (NRPOPs) with a combination of sulfur or oxygen heteroatoms, which possess ultra-small pores within the frame apertures. In certain exemplary embodiments, their highly selective CO2 adsorption properties make these polymers, promising candidates in making suitable gas separable membranes or heterogeneous catalysts.
In certain exemplary embodiments, chemically and thermally stable nitrogen-rich porous organic polymers (NRPOPs) and method of synthesis thereof are provided. The NRPOPs have ultra-small pore apertures and can be utilized in the formation of membranes for use in membrane-based gas separation technology.
According to another exemplary embodiment of the invention, the NRPOPs have nitrogen heterogeneity which provides an alkaline environment to the polymer and any membrane formed utilizing the polymer and can enhance the sorption of acidic gases, such as carbon dioxide (CO2).
According to still another exemplary embodiment of the invention, a separation membrane system and process is provided utilizing NRPOPs for the separation of acidic CO2 from an input gas stream to produce a purified gas stream that can function as a renewable energy fuel. The system and process of the invention can additionally reduce transportation costs as a result of the ease of implementation of the system and process, increasing the heat value of the output natural gas/methane gas stream thereby increasing the environmental benefits of the system and method. The membrane-based separation system and process, utilizes one of a number of nitrogen-rich porous organic polymers which contain ultra-small pores in their structures to form a simpler, easy to regenerate separation system and method that does not involve phase changes in the operation of the system.
According to another exemplary embodiment of the invention, functionalized nanoporous organic polymer(s) or NRPOP(s) are provided for use as: a) nanoporous membrane composite(s) for CO2 gas separation and b) heterogeneous catalysts to convert CO2 to useful chemicals. Because of the heteroatomic surface functionality in the NRPOPs, these polymers are also attractive in preparation of heterogeneous catalysts.
According to still another aspect of an exemplary embodiment of the invention, composition of matter includes a porous organic polymer having ultra-small pores defining apertures therein, wherein the structure of the polymer forming the pores is nitrogen-rich, sulfur-rich, oxygen-rich, or a combination thereof.
According to still another aspect of an exemplary embodiment of the invention, a method for removing carbon dioxide gas from an input gas stream includes the steps of providing a porous organic polymer having ultra-small pores defining apertures therein, wherein the structure of the polymer forming the pores is nitrogen-rich, sulfur-rich, oxygen-rich, or a combination thereof, passing the input gas stream through the composition and removing carbon dioxide gas molecules from the input gas stream.
According to still another aspect of an exemplary embodiment of the invention, a method for initiating a catalytic CO2 conversion reaction includes the steps of providing a porous organic polymer, wherein the structure of the polymer forming the pores is nitrogen-rich, sulfur-rich, oxygen-rich, or a combination thereof, reacting the polymer composition with a transition metal to form a heterogeneous catalyst; and placing the heterogeneous catalyst in catalytic conversion reaction of CO2 to useful chemicals.
Numerous other aspects, features, and advantages of the invention will be made apparent from the following detailed description.
The drawing figures illustrate the best mode currently contemplated of practicing the present invention.
In the drawings:
Reference will now be made in detail to various embodiments of the invention, one or more examples of which are illustrated in the accompanying drawings. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that modifications and variations can be made in the present invention without departing from the scope and spirit thereof. For instance, features illustrated or described as part of one embodiment may be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
Development of solid sorbents to separate gas molecules, and in one embodiment to separate carbon dioxide from methane and nitrogen, has recently attracted considerable interest in an effort to treat pre-combustion or post-combustion gases, for example, natural gas, landfill gas or flue gas. In certain exemplary embodiments of the invention, heteroatom (N,S,O)-rich porous organic polymers (POPs) which contain ultra-small pores (subnanometer size) in their structures have been developed for this purpose. Four different types of polymers were synthesized with varying heteroatoms (C, N, O and S) in their structures.
In one exemplary embodiment, nitrogen-rich phenazine-linked polymers (PLPs) were synthesized by condensation reaction between ortho-diamine and ortho-diketone (
General Techniques, Materials, and Methods.
All chemicals were purchased from commercial suppliers (Sigma-Aldrich, Acros Organics, and Frontier Scientific) and used without further purification, unless otherwise noted. Air-sensitive samples and reactions were handled under an inert atmosphere of nitrogen using either glovebox or Schlenk line techniques. FT-IR spectra were obtained using Attenuated Total Reflectance sampling on PerkinElmer FT-IR spectrometer. Sorption experiments were collected using a NOVA-1000 series analyzer using adsorbates of UHP grade. In a typical experiment on a polymer sample, the sample was loaded into a 9 mm large bulb cell of known weight and then hooked up to NOVA series analyzer and degassed at 120° C. for 12 h. The degassed sample was refilled with nitrogen, weighed precisely and then transferred back to the analyzer. The temperatures for adsorption measurements were controlled by using refrigerated bath of liquid nitrogen (77 K), or a temperature controlled water bath (273K, 288K, 298K and 313K). Carbon dioxide (CO2) and methane (CH4) isotherms were collected at 273, 288, 298 and 313K. Nitrogen (N2) isotherms were collected at 77, 273, 298 and 313K. Pore Size Distribution (PSD) was calculated using NLDFT model (on carbon). PSD mesoporous (2 nm to 50 nm) and microporous (less than 2 nm) regions were calculated from nitrogen (N2) isotherm collected at 77 K, while the PSD in ultra-micropore (0.35-1.5 nm) region was estimated from carbon dioxide (CO2) isotherm collected at 273K.
Synthesis of PLP-1.A 100 mL Schlenk flask was charged with stoichiometric amount of hexaketocyclohexane and 3,3′-diaminobenzidine and refluxed in acetic acid for 3 days to form the polymer according to the reaction scheme in
PLP-1 (C48H18N12.5H2O): Calcd. C, 67.60%; H, 3.31%; N, 19.71%.
Found: C, 67.52%; H, 3.03%; N, 18.35%.
Synthesis of GDP-1.A 100 mL Schlenk flask was charged with stoichiometric amount of melamine and glyoxal, and refluxed in DMSO for 3 days to form the polymer according to the reaction scheme in
GDP-1 (C12H6N12.C4H12O2S2): Calcd. C, 40.50%; H, 3.82%; N, 35.42%.
Found: C, 42.94%; H, 3.05%; N, 33.66%.
Synthesis of BOLP-1.A 100 mL Schlenk flask was charged with stoichiometric amount of amine 1, 4-Benzenediol, 2,5-diamino-, hydrochloride (BDODAH) and 1,3,5-Triformylbenzene (TFB), and refluxed in anhydrous DMF for 3 days to form the polymer according to the reaction scheme in FIG. 3. The solid product was filtered, washed with tetrahydrofuran and finally dried at 150° C. under vacuum overnight. A light brown colored solid product was obtained in high yield (91%) with the following exemplary composition:
BOLP-1 (C36H12N6O6.2H2O): Calcd. C, 65.46%; H, 2.44%; N, 12.72%; O, 19.38%.
Found: C, 65.06%; H, 4.01%; N, 11.74% O, 19.13%.
Synthesis of BTLP-1.A 100 Schlenk flask was charged with stoichiometric amount of amine 1, 4-Benzenedithiol, 2,5-diamino-, hydrochloride (BDTDAH) and 1,3,5-Triformylbenzene (TFB), and refluxed in anhydrous DMF for 3 days to form the polymer according to the reaction scheme in
BTLP-1 (C36H12N6.5H2O): Calcd. C, 57.12%; H, 2.13%; N, 11.10%; S, 25.42%.
Found: C, 57.78%; H, 2.83%; N, 10.91% S, 20.72%.
Results and DiscussionPhenazine-linked polymer (PLP-1), glyoxal-derived polymer (GDP-1), benzoxazole-linked polymer (BOLP-1), and benzothiazole-linked polymer (BTLP-1) were synthesized by the exemplary embodiments for the polycondensation reactions as shown in
The chemical connectivity within the polymers was investigated by FT-IR spectroscopic technique. Spectra were measured for the starting monomers and are depicted along with the spectra for PLP-1 in
FT-IR spectra for GDP-1 and the starting monomer melamine are depicted in
FT-IR spectra for BOLP-1 and the starting monomers are depicted in
FT-IR spectra for BTLP-1 and the starting monomers are depicted in
Physical, morphology of the polymer was studied via Scanning Electron Microscopic (SEM) images (
Powder X-ray diffraction analysis was performed to understand the crystallinity of the polymers (
The porous nature of the synthesized polymers was studied by nitrogen sorption-desorption isotherms collected at 77 K.
The carbon dioxide (CO2) isotherm at 273K from
In order to understand the effect of the nitrogen heterogeneity in porous frames and the ultra-small pore size distribution in selective gas adsorption capacity, a series of polymers were synthesized varying the frame heteroatoms and the building units. Melamine is an economically cheap and fascinating building unit which provides high content of nitrogen through amine functional groups. Glyoxal which is the shortest aldehyde monomer among the dialdehyde series was reacted with melamine in a second exemplary embodiment to synthesize glyoxal-derived polymer (GDP-1) according to the scheme in
In third exemplary embodiment, a benzoxazole-linked polymer (BOLP-1) was synthesized, which provides oxygen heterogeneity in the frame along with the nitrogen atoms, as shown by the
Having significantly improved surface areas and higher micropore distribution, we attempted to synthesize an analogue of BOLP-1 using thiazole linker instead of oxazole linker. Benzothiazole-linked polymer (BTLP-1) provides sulfur heterogeneity in the frame instead of oxygen along with the nitrogen atoms, as shown by the
Although the synthesized polymers have a significant nitrogen atom constituency, significant differences in surface areas and PSD are expected to play important roles in gas uptake properties. Looking at Table 1, PLP-1, GDP-1, BOLP-1 and BTLP-1 possess carbon dioxide (CO2) adsorption to 63, 85, 175 and 99 mgg−1, respectively, at 273 K and 1 bar. Highest CO2 uptake for BOLP-1 is consistent with its highest surface area and is in the top list of reported porous organic polymers. Surprisingly, PLP-1 which possesses surface area of only 24 m2g−1, adsorbs significant amount of CO2 (63 mgg−1 at 273 K). This is due to the presence of high percentage of ultra-micropores which are large enough for free passage of CO2 gas molecules. On the other hand, N2 gas molecules because of their slightly larger kinetic diameter are not suitable to enter within the ultra-micropores, resulting in significant drop in the surface areas estimated from N2 adsorption isotherm. Smaller pores in PLP-1 also facilitate the stabilization of adsorbed carbon dioxide (CO2) gas molecules, which pay off the significant lower surface area. However, the carbon dioxide (CO2) uptake per unit surface area (Table 1) for PLP-1 surpasses any porous organic polymers so far reported, which indicates the superiority of the PLP-1 over other porous organic polymers.
In order to understand the high carbon dioxide (CO2) affinity for the surface of PLP-1, GDP-1, BOLP-1 and BTLP-1, isosteric heats of adsorption (QST) have been calculated using the virial method from the isotherms measured at 273 and 298K and are illustrated in
Given the high carbon dioxide (CO2) uptake per unit surface area, and desirable binding affinity, the selective carbon dioxide (CO2) capture over methane (CH4) gas and nitrogen (N2) gas (
In order to be industrially applicable for carbon dioxide (CO2) separation from an input gas, such as a flue gas or landfill, gas, the regeneration properties of PLP-1, GDP-1, BOLP-1 and BTLP-1 were evaluated, for carbon dioxide (CO2) at 298 K. The results shown in
High gas adsorption selectivity and easy regeneration properties are the attractive features for using the synthesized NRPOPs in making efficient membrane composites for gas separation applications. The membrane composites of these NRPOPs can be formed in a known manner such by direct casting the NRPOPs on flat glass plates or using spin coating methods. In a typical exemplary process, the NRPOP(s) can be suspended in a suitable matrix (e.g. polysulfone) dissolved in a suitable solvent (e.g. chloroform). The resulting suspension is then cast onto a flat glass plate to form the membrane composite, which is subsequently dried under vacuum at 100° C. overnight to obtain the membrane composites. Third method is the casting of membrane composite inside a fritted disk. Resulting doped frit is dried under vacuum at 100° C. overnight to obtain the frit doped with membrane composites.
The membrane composites formed in these and other manners can be tested for usefulness in gas separation by connecting the membrane between a gas mixture supply and a portable gas sensor. Gas from the gas mixture supply, such as a 50:50 mixture of methane and carbon dioxide, is passed into an inlet for the membrane assembly and the output is connected to the gas sensor to determine the amount of carbon dioxide retained by the membrane.
In addition to chemical and thermal stability, the heteroatomic surface functionality made the polymers attractive in preparation of heterogeneous catalysts using various compounds, such as various metal nanoparticles, including transition metal nanoparticle in certain exemplary embodiments, bonded to the support structure provided by the heteroatom (N,S,O)-rich porous organic polymers. Catalytic conversion of CO2 to propiolic acid derivatives using silver nanocatalyst is a promising way to convert CO2 to useful chemicals. Heteroatomic functionality, particularly, the presence of sulfur (S) BTLP-1 is expected to stabilize the silver nanocatalysts through the stable S→Ag dative bond. Synthesized BTLP-1 is used for the preparation of stable silver nanocatalyst (Ag@BTLP-1). In a typical preparation of nanocatalyst, activated BTLP-1 powder is immersed in acetonitrile containing silver nitrate (AgNO3) and the mixture is then stirred at room temperature. After the impregnation, the suspension is centrifuged and the solid is dried at 100° C. under vacuum for overnight and then finally chemically reduced by NaBH4. Resultant nanocatalyst is then dried and used in CO2 catalytic reaction as shown in
The following references are expressly incorporated by reference herein in their entirety for all purposes.
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Various other embodiments of the invention are contemplated as being within the scope of the filed claims particularly pointing out and distinctly claiming the subject matter regarded as the invention.
Claims
1. A composition of matter comprising a porous organic polymer having pores defining apertures that are less than 1.5 nm in diameter therein, wherein the polymer is a phenazine-linked polymer (PLP), a glyoxal-derived polymer (GDP) or a benzothiazole-linked polymer (BTLP).
2. The composition of claim 1 wherein the pores have an average diameter of between 0.25 nm and 0.6 nm.
3. The composition of claim 1 wherein the pores have an average diameter of between 0.35 nm and 0.5 nm.
4. The composition of claim 1 wherein the composition includes at least one of nitrogen, sulfur and oxygen heterogeneity in the structure of the polymer surrounding the pores.
5. The composition of claim 4 wherein the composition is a component of a gas separation membrane.
6. The composition of claim 5 wherein the composition has a measured adsorption selectivity for carbon dioxide (CO2) molecules over methane (CH4) molecules of at least 10.
7. The composition of claim 6 wherein the composition has a measured adsorption selectivity for carbon dioxide (CO2) molecules over methane (CH4) molecules of at least 19.
8. The composition of claim 6 wherein the composition has a measured adsorption selectivity for carbon dioxide (CO2) molecules over nitrogen (N2) molecules of at least 40.
9. The composition of claim 5 wherein the composition has a measured adsorption selectivity for carbon dioxide (CO2) molecules over nitrogen (N2) molecules of at least 80.
10. The composition of claim 9 wherein the composition has a measured adsorption selectivity for carbon dioxide (CO2) molecules over nitrogen (N2) molecules of at least 100.
11. The composition of claim 4 wherein the composition is heterogeneous catalyst.
12. The composition of claim 1 wherein the composition has the following formula:
13. (canceled)
14. The composition of claim 1 wherein the composition has the following formula:
15. The composition of claim 1 wherein the composition has the following formula:
16. A method for removing carbon dioxide gas from an input gas stream, the method comprising the steps of:
- a) providing the composition of claim 1;
- b) passing the input gas stream through the composition; and
- c) removing carbon dioxide gas molecules from the input gas stream.
17. The method of claim 16 wherein the step of removing the carbon dioxide gas molecules from the input gas stream comprises adsorbing the carbon dioxide molecules onto the composition.
18. The method of claim 17 further comprising the steps of:
- a) desorbing the carbon dioxide molecules from the composition; and
- b) passing additional input gas through the composition to adsorb additional carbon dioxide molecules onto the composition.
19. A method of initiating a catalytic conversion reaction; the method comprising the steps of:
- a) providing the polymer composition of claim 1;
- b) reacting the polymer composition with a transition metal to form a heterogeneous catalyst; and
- c) placing the heterogeneous catalyst in contact with reactants to catalyze the CO2 conversion reaction.
20. The method of claim 19 wherein the composition includes at least one of nitrogen, sulfur and oxygen heterogeneity in the structure of the polymer surrounding the pores.
Type: Application
Filed: Mar 20, 2017
Publication Date: Sep 20, 2018
Patent Grant number: 10150096
Inventor: Mohammad G. Rabbani (Platteville, WI)
Application Number: 15/463,141